Insecticidally active acylated beta,beta,beta-trichloro-alpha-(3,4-dichlorophenyl)-ethanol

ABSTRACT

COMPOSITIONS AND METHODS OF USING CERTAIN ACYLATED B,B,B - TRIHALO - A - (3,4-DICHLOROPHENYL)-ETHANOLS OF THE GENERAL FORMULA   1,2-DI(CL-),4-(R-COO-CH(-C(-X)3)-)BENZENE   IN WHICH: X IS BROMINE, CHLORINE OR FLUORINE, AND R IS LOWER ALKYL, WHICH POSSESS STRONG INSECTICIDAL PROPERTIES. MOST OF THE ACYLATED SUBSTITUTED ETHANOLS ARE NEW COMPOUNDS.

United States Patent Oflice 3,801,712 INSECTICIDALLY ACTIVE ACYLATED 5,;8,18-TRI- CHLORO-a-[S,4-DICHLOROPHENYL]-ETHANOL Werner Meiser, Wuppertal-Elberfeld, Wolfgang Behrenz, Cologne, and Karl-Heinz Buchel, Wuppertal-Elberfeld, Germany, assiguors to Bayer Aktiengesellschaft, Leverkusen, Germany No Drawing. Filed June 22, 1971, Ser. No. 155,601 Claims priority, application Germany, Mar. 3, 1970, P 21 10 056.1; June 26, 1970, P 20 32 076.7 Int. Cl. A01n 9/24 US. Cl. 424311 5 Claims ABSTRACT OF THE DISCLOSURE Compositions and methods of using certain acylated [3,5,5 trihalo a [3,4-dichlorophenyl]-ethanols of the general formula in which:

X is bromine, chlorine or fluorine, and R is lower alkyl,

which possess strong insecticidal properties. Most of the acylated substituted ethanols are new compounds.

The present invention relates to and has for its objects the provision of particular new active compositions in the form of mixtures with solid and liquid dispersible carrier vehicles of certain acylated B,B,;8-trihalo-a-[3,4-dichlorophenyl]-ethanols which possess valuable strong insecticidal properties, and methods for using such compounds in a new way for combating and controlling insects with other and further objects becoming apparent from a study of the within specification and accompanying examples,

It is already known that p,/3,;3-trichloro-u-[3,4-dich1orophenyl]-ethano1 exhibits insecticidal properties (R. Riemschneider, Monatshefte fiir Chemie, vol. 82 (1951), pages 600-606; Swis Patent Specification 251 120). Furthermore, it is known that fl,;3,B-trichloro- -(4-chlorophenyl)-ethanol and its acetyl derivative exhibit insecticidal properties (German patent specifications 673,246

and 706,111). These compounds, however, are not particularly effective (cf: Linger, Martin, Miiller, Helv, Chim. Aceta, vol 27, page 892( 1944) It has now been found that the acylated p,}3,B-triha1o-a- [3,4-dichlorophenyl]-ethano1s of the general formula:

01 CH-O-C O-R in which:

X is bromine, chlorine or fluorine, and R is lower alkyl,

exhibit excellent insecticidal properties.

I, Patented Apr. 2,1974

The inventiontherefore provides an insecticidal com position containing as active ingredient a compound of Formula I in admixture with a solid diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.

The invention also provides a method of combating insects which comprises applying to the insects or a habitat thereof a compound of Formula I alone or in the form of a composition containing as active ingredienta com pound of Formula I in admixture with a solid or liquid diluent or carrier.

The invention also provides crops protected from dam age by insects by being grown in areas in which, immediately prior to and/or during the time of the growing, a compound of Formula I was applied alone or in admixture with a solid or liquid diluent or carrier. By this means the usual methods of providing harvested crops may be improved.

Surprisingly, the acylated carbinols of the FormulaI, especially 5,3,3 trichloro' a[3,4-dichlorophenyl]-ethy1- acetate, compared with the known, non-acylated 13,13,3- trichloro-a-chlorophenyl-substituted carbinols and 5,13, 3- trichloro-a-(4-chlorophenyl)-ethyl acetate, possess a far superior insecticidal elfectiveness, especially against flies, mosquitoes and bugs. The eifect sets in vary rapidly and is long-lasting.

The compounds can therefore be used with good re sults for the control of insects, particularly Diptera, their low toxicity to warm-blooded animals being of particular advantage. Thus, tests indicate that fl,fi,B-tIlChIOI'O-ot-[ 3,4- dichlorophenyl]-ethyl acetate has a median toxicity value (LD greater than 2500 mg./ kg. rat (oral) Furthermore, the compounds to be used according to the invention, compared with the standard preparation dichlorodiphenyltrichloroethane, possess the advantage of better and more rapid effectiveness as well as higher vapor pressure, so that fewer residue problems result. They can therefore replace DDT which is increasingly losing its importance; The substances to be used according to the invention therefore represent in many respects a genuine enrichment of the art. 1 a

As examplesof compounds. of Formula I to be used according to the inventionthere are preferred those wherein X is chlorine and Rismethyl, ethyl, propyl,-.isopro'pyl, butyl, tert.-butyl and l-ethylpropyl, in particular:- wt

3,13,)3-trichloro-d-[3,4-dichlorophenyl]-ethyl Z-methyl v 13,3,5-tribromo-d-[3,4-dichlorophenyl] ethyl Z-methyl propionate, I fl,;3,,8-tribromo-a-[3,4-dichlorophenyl]-ethyl 2-dimethyl propionate, '1 fl,B,,6-trifluoro-a-[3,4-dichloropheny1jethy a q,

Ofthe active compounds" which are used according to the invention fi,;9,}3 tIiChlOTO-a- 3,4 dichlorophenyl]-ethyl "acetate has been prepared by R. Riemschneider, Monatt 3 shefte fiir Chemie, vol. 82, compounded Formula I, however, are new, i.e. those wherein not all Xs are chlorine or where R is other than methyl.

' These compounds can be prepared according to known processes, especially by acylation of the appropriate carbinols with acid anhydrides or chlorides, possibly in the presence of acid-binding agents or in the presence of catalytic amounts of acid, as for example sulfuric acid. The reaction product may be isolated by destroying the excess acid chloride or anhydride by hydrolysis, separating the aqueous layer and purifying the resulting organic phase by distillation or crystallization.

Preparation of the carbinols to be used as starting materials may be effected either by Friedel-C'rafts acylation of the appropriate hdyrocarbons with trihaloacetaldehydes with catalytic assistance of AlCl FeCl BF or concentrated H2504 pursuant to J. W. Howard, J. Amer. Chem. Soc. vol. 57, p. 2317 (1937), T. C. Chen and W. T. Sumerford, J. Amer. Chem. Soc. vol. 72, pp. 5 124-5.,(1950), or P. Crooy, 1nd. Chim. Belge, vol. 32, pp. 268-271 (1967), or according to other processes as disclosed by J. W. Howard and G. N. Stephens, J. Amer. Chem. Soc. vol. 60, p. 228 (1938), R. Riemschneider, Monatschefte fiir Chemie, vol. 82, pp. 600-606 (1951), or Swiss patent specification 258,755). As already mentioned, the substances which can be used according to the invention are distinguished by outstanding insecticidal properties. They possess a good effectiveness against both sucking and biting insects, as wellas, above all, against Diptera. 1

The products are therefore used with success in crop protection and the protection of stored products as well as in the hygiene field against the most diverse animal pests.

, To thesucking insects contemplated herein there belong, in the main, aphids (Aphidae) such as the green peach aphid (Myzus persicae), the bean aphid (Doralis fabae), the bird cherry aphid (Rhopalosiphum padi the pea aphid (Macrosiphum pisi) and the potato aphid (Machrosiphum solanifolii), the current gall aphid (Cryptomyzus -korschelti),-': the rosy apple aphid: (Sappaphis m'ali), the mealy plum aphid (Hyalopterus arundinis) and the cherry blackfly '(Myzus cerasi); in addition, scales and mealybugs (.C'occinq); for example the 'oleander scale '(Aspidioms hederae) .and' the soft scale (Lecanz'um hesperidum) as well-as the'grape mealybug' (Pseudocaccus maritimus); thrips (Thysanoptera), such as Hercinot'hrips femoralis, and bugs, for example the beet bug (Piesma quadrata), the red cotton bug (Dysdercusintermedius), the bed bug (Cimex lectular'ius), the assassin bug (Rhodnius prplixus) and Chagas bug (Triatoma infestans) and, further, cicadas, such as Eusclis bilobatus and Nephotettix bipunctatus; and the like.

In the case ofthe biting insects contemplatedv herein, above all there should be mentioned butterfly caterpillars (Lepidoptelfa) such as the diamond-back moth (Plutella maculipen nis), the gypsymoth (Lymantria dispar), the browntail moth '(Euproctischrysorrhoe'a) and tent caterpillar (Malacosoma neustria); further, the cabbagemoth (Mamestra, brasricae) ,and the cutworm (Agrotis segetum'), the large white butterfly (Pieris br assz'cae), the small winter moth (Cheimatobia brumata), the green oak tortix moth. (Iortrix viria ana), the fall armyworm (Laphygma frugiperda) and cotton worm (Prodenia litum), the ermine moth (Hyponomeu tal padella), the Mediterranean flou1? 1noth(Ephestia kiihniella) and greater wax' moth (Galleria mellonella); and the like.

Also to be classed with the biting insects contemplated herein are beetles (Coloptra), for example the granary weevil (Sitophilus granarius=Calandra granaria), the Colorado beetle (Leptinotarsq decemlineqta), the dock 5 p.- 0 h o he 7 the raspberry beetle (Byturus tomentosus), the bean weevil (Bruchidius=Acanthoscelides obtectus), the beetle (Dermestes frischi), the khapra beetle (Trogoderma granarium), the flour beetle (Tribolium castwmeumz), the northern corn billbug (Calandra or Sitophilus zeamais), the drugstore beetle (Stego'bt'um paniceum), the yellow mealworm-(Tenebrio molitor) and the saw-toothed grain beetle (OryZaephiZus surinamensis), and also species living in the s0il,f0r example wireworms (Agriotes spec.) and larvae of the ,cockchafer (Melolontha melolonrha); cockroaches, such as the German cockroach (Bla ttella germunica), 'American cockroach (Periplaneta amencana), Madeira. cockroach (Leucophaea or Rhyparobia nm-deirae), oriental cockroach (Blatta orien'lalis), the giant cockroach (Blaberus giganteus) and the black giant cockroach (Blaber'ws fuse-us) aswell as Henschouted'enia flexivz'tta; further, Orrhoptera, for example the house cricket (Acheta domesticus); termites such as the eastern subterranean termite (Reticulite'rmes flavipes) and Hymenoptera such as ants, for example the garden ant (Lasiu-s niger); and the like.

The Diptera contemplated herein comprise essentially the flies, such as the vinegar fly (Drosophila melanogaster), the Mediterranean fruit fly (Ceratitis capitata), the house fly (Musca domestica), the little house fly (Fannia canicularz's), the black blow fly (Phormia aegina) and bluebottle fly (Calliphora erythrocephala) as well as the stable fly (Stomvxys calcitrans); further, gnats, for example mosquitoes such as the yellow fever mosquito (Aedes aegypti), the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles stephensi); and the like.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents, carriers or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/ or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for

example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as Freon; .inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), paraffins (e.g. petroleum fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, etc.), amines (e.g. ethanolamine, etc.), ethers, ether-alcohols (e.g. glycol monomethyl ether,

8 etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), ketones (e.g. acetone, etc.), and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, clays, alumina, silica, chalk, i.e. calcium carbonate, talc, attapulgite, montomorillonite, kieselguhr, etc.)

and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for

beetle (Gastrophyra 'viridula), the mustard beetle (Phaee, don cochleariae), the blossom beetle (Meligethes aeneus),

this purpose: emulsifying agents, such as non-ionic and/ or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty leather,

alcohols, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl arylpolyglycol ethers, magnesium 'stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other acaricides, insecticides, fungicides, bactericides and nematocides, or rodenticides, herbicides, fertilizers, growth-regulating agents, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marked preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 01-95% by weight, and pref erably 05-90% by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0001-%, preferably 0.01-1%, by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprise mixtures of a conventional dispersible carrier vehicle such as (1) a dispersible inert finely divided carrier, solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective forthe purpose in question and which is generally between about 0.0001-95%, and preferably 0.0195%, by weight of the mixture.

The active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very elfective atomizing equipment, in finely divided form, e.g. average particle diameter of from 50-100 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about to 1000 g./hectare, preferably 40 to 600 g./hectare, are suflicient. In this process it is possible to use highly concentrated liquid compositions. with said liquid carrier vehicles containing from about to about 95% by weight of the active compound or even the 100% active substance alone, e.g. about 20-100% by weight of the active compound. r

Furthermore, the present invention contemplates methods of selectively killing, combating or' controlling pests, e.g. insects, which comprises applying to at least one of (a) such insects, and (b) the corresponding habitat thereof, i.e. the locus to be protected, a correspondingly combative or toxic amount, i.e. an insecticidally effective amount of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance 'by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring, fumigating, and the like.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding activity of the particular new compounds of the present invention are illustrated, without limitation, by the following examples and their tables wherein h. means hours and means minute s.

. EXAMPLE1. LT test'for-Dipteraz Test insects: Musca domestica Solvent: acetone i 2 parts by weight of activecompound are dissolved in 1000 parts by volume of solvent. The solution so obtained is diluted with further solvent to the desired lower concentrations. I

2.5 ml. of the solution of active compound are pipetted into a Petri dish. On the bottom of the Petri dish there is a filter paper with a diameter of about 9.5 cm. The Petri dish remains uncovered until the solvent has completely evaporated. The amount of 'activecompound per square meter of filter paper varies with the concentration of the solution of active compound used. About 25 test insects are then placed in the Petri dish and it is covered with a glass lid.

The condition of the test insects is periodically observed. The time which isnecessary fora 100% destruction is determined.

The testinsects, the active compounds, the concentrations of the active compounds and the periods of time at which there is a 100% destruction can be seen from the following Tablel. p I

TABLE 1 (LTroo test for Dlptera) Concentration of active compound ar SO 11 011 Active compound in percent Llm -on-o o 0 cm 0 8 0% (known) ol--on o-ooom o p 8 h 90% (1)..-- Cl 0. 2 30 0 088 8 01 amp-coon;

(2)..-- Cl 7 0. 2 0.04 8 h.

01 OH-O-C O C2Hs (3)--.. Cl 0.2 a 75 0% 8 h 50 Cl oH-o-o 0on1,

EXAMPLE 2 1T test for Diptera:

Test animals: Aeaes aegypti Solvent: acetone into a Petri dish. 0n the bottom of the Petri dish there is a filter paper with a diameter "of about 9.5 cm. The Petri dish remains uncovered until the solvent has com pletely evaporated. The amount of active compound per square meter of filter paper varies with the-concentration of the solution of active compound used. About"25 test insects are then placed in the Petri dish and it is covered witha g'lass lid.

The condition of served. The time which 'is' necessary for a tion is determined.

The test' insectsjth e active compounds. the concentrations of theactive compounds andfthe P fiQ S of; time at which thereis a 100% destruction canfbe seen from the following Table 2.

theftest insects is "periodically ob l% jde'st r"ucuse v (LT ootest for dipt erw i A Concentration' i. active compound j in the i solution Active compound I I in percent. LTXOO (B)..- 0.2 15 C1 CH-O-COCHa 0.04 15 J 0. 00s 75' Cl:' r j 0.0016 4h.=20%

(known). I (A).-. 0.2 4h.=

QUE-O-COCH: 0%

(known). 0 con 0.2 i 45 1 0-04. 0 o1- 01 0.008 4 n. =so%- (known).

(1)-..- G1 0.2 15' l 0.04 15' 0.00s 45' Cl- CH--O'COCH: 0. 001g 4 h =so% 0&1.

EXAMPLE 3 I LT test for Diptera:

Test insects: Anopheles atroparvus I Solvent: acetone 2 parts by weight of active compound are dissolved in 1000 parts by volume of solvent. The solution so obtained is diluted with further solvent to the desired lower concentrations. i} V 2.5 m1. of the solution of active compound are pipetted into a Petri dish. On the bottom of the Petri dish there is a filter paper with-a diameter of about 9.5 cm. The Petri dish remains uncovered until the solvent has completely evaporated. The amount of active compound per square meter of filter paper varies with the concentration of the solution of active compound used. About 25 testinsects are then placed in the Petri dish and it is covered with a glass;1id.

The condition of the test insects is periodically ob-' served. The time which is necessary for a 100% destruction is determined. The test insects, the active compounds, the concentrations of the active compounds and the periods of time at 8 whichthere is a destruction can be seen from the following Table I TABLE?) LT100 test for Diptera I Concentration of active compound in the solution in i .Active compound 1 percent LTn' o (o) con 1 I 0.2 Y 60' p 004- v 60 01+ Cl 0.00s 90 I nown). v (A)--. 0.2'

CHOCO-CH3' (known). w -i (1)-... 01" 0.2 15' v 0.04 30' 0.00s 45' c1 CHO-CO'CH3 J i v I jean v (2),.-. Cl i 0.2 15' 0. 04 30' 0.008 75'. 01- -CH-OCOC2H6 The following further examples are set forth to illustrate, without limitation, the process for producing the active compounds according to the present invention.

EXAMPLE 4 Cl (3-0-0 O-CH2CIIJ 150 ml. of propionic'anhydride are added to 147 gfiolf fi,/3,fi-tri ch1oro-a-[3,'4=dichlorophenyl] ethanol in 100 m1. of glacial acetic acid, and to this mixture 102 g. of concentrated sulfuric acid are added dropwise at 80 C. The

reaction mixture is then-heated on a water-bath for an hour; after cooling, it is poured into ice water; one hour later,'it is taken up-in methylene chloride and the organic 118g. of butyric anhydride are added to 94 g. of 3,5,6- trichloro-ot-[3,4-dichlorophenyl]-ethanol in 65 ml. of glacial acetic acid, and to this mixture 65 g. of concen-. trated sulfuric acid are added dropwise at about 80 C. The mixture is then heated on a water-bath for an hour; after pouring into 1 liter of ice water, it is extracted .with methylene chloride one hour later and the organic layer is dried. The solvent is evaporated under reduced pressure, theresidueis distilled, and the butyrat e of 3, 3,13- trichIOro-a-I3,4-dichlorophenyl]-ethanol is obtained in an amount of 95 g. with the BF. C./ 0.4 mm. Hg.

The compounds of Formula I whose substituents are listed in the following table can be obtained in a manner analogous to that of the above examples.

It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention.

What is claimed is:

1. The method of controlling insects which comprises applying to said insects or their habitat an insecticidally effective amount of an acylated ethanol of the formula in which R is methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl or l-ethylpropyl.

2. The method of claim 1 wherein such insects are Diptera.

3. The method of claim 1 wherein such acylated eth- 10 anol is p,p,p3-trichloro-a-[3,4-dichlorophenyl]-ethyl acetate of the formula Ch 4. The method of claim 1 wherein such acylated ethanol is B,p,p-trichloro-u-[3,4-dichlorophenyl]-ethyl propionate of the formula H c-o-oo-cm-cm 5. The method of claim 1 wherein such acylated ethanol is p,p,p-trichloro-a-[3,4-dichlorophenyl] -ethyl butylate of the formula H C-O-C O-GHz-CHr-CH:

(3) References Cited UNITED STATES PATENTS 2,508,335 5/1950 Moyle et al. 424311 2,861,097 11/1958 Senkbeil et a1 7l106 X FOREIGN PATENTS 673,246 3/ 1939 Germany. 706,111 1/1952 Germany.

OTHER REFERENCES Chemical Abstracts, vol. 43, item 7959i, 1949.

J. Amer. Soc., vol. 72, pp. 5124-24, November 1950.

J. Amer. Chem. Soc., vol. 77, pp. 541041, October 1955.

ALBERT T. MEYERS, Primary Examiner D. W. ROBINSON, Assistant Examiner US. Cl. X.=R. 260-488 CD z gg q "U'Ni 'i'i51) O MCE A CERTIFICATE OF CORRECTION Patent No. 3,801,712 Dated April 2, 1974 Immm) WERNER MEISER ET AL It is certified that error appears-in the aboye-idcntified patent and that said Letters Patent are hereby corrected as shown below:

(301. 1, line 8 (Priority Claim) change "Mar. 3, 1970" to '7 Mar 3, '1971".

. Col. 1, line 48, correct spelling of "Swiss".

Col. 2, line 49, before "butyrate" insert ethyl Col. 3, line- 41, correct spelling of "Macrosighum".

Col. 3, line 42, correct spelling of "currant".

Col. 3, line 65, correct spelling of "tortrix' Signed and sealed this 22nd day of October 1974.

(SEAL) Attest:

MeCOY M. GIBSON JR. 0. MARSHALL DANN Attesting'qfficer Commissioner of Patents 

